Synthesis of Aminocyclopropanes by Redox‐Neutral Aminoalkylation

A redox‐neutral hydroaminoalkylation strategy has been developed for the synthesis of 1,1‐disubstituted aminocyclopropanes from alkenes and alkynes. Through simple solvolysis activation, the reaction of an easily accessible, bench‐stable hemiaminal precursor allows excellent yields of the target products at ambient temperature. The approach presented herein has a substrate tolerance that is orthogonal to classical aminocyclopropane syntheses, and its deployment for the preparation of bioisosteres of pharmacologically active gem ‐α‐dimethylamines resulted in improved biological properties.